JPH07309728A - Hair cosmetic composition - Google Patents

Abstract

PURPOSE:To obtain a hair cosmetic composition which contains, as essential ingredients, an amphoteric macromolecular compound of a specific molecular weight and an oily oligomer of a specific molecular weight, thus can give hairs an elastic touch without stiffness or starchiness in the form of spray, dispenser or foam. CONSTITUTION:This composition comprises an amphoteric macromolecular compound of 50,000-500,000 molecular weight, represented by formula I (n, m are natural numbers wherein n/m is 70/30 20/80; R1, R5 are H, methyl; R2, R3 are alkyl; R4, R7 are alkylene; R<6> is an alkyl; A is O, NH) and a water-soluble oily oligomer of formula II (p, q are natural number wherein p/q is 9/1-1/9). The composition can be prepared into a hair-dressing agent to give hair elastic touch without stiffness, after it is applied, manifest high hair-setting power and hair set-holding power under high humidity with heavily suppression of flaking formation and form coating film of desirably high hardness on the hair surface.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hair cosmetic composition, the purpose of which can be prepared as a spray-type, dispenser-type, or foam-type hair styling agent, and the elasticity of the hair after application does not cause stiffening. A hair makeup that imparts a certain texture, has good setting force and set retention under high humidity, hardly causes flaking, and can form a film having good hardness on the surface of hair. To provide a food composition.

[0002]

2. Description of the Related Art Hair styling agents have been used in the past for preparing hairstyles and for making set hairstyles last longer. Hair styling products can be classified into oil-based hair styling products, liquid hair styling products, and hair styling products containing high molecular substances when they are classified based on the raw material base, and all of these products cover the outside of the hair and adhere to it to improve the hairstyle. To hold. Japanese people with hard hair have used oil-based hair styling products such as pomade and hair oil, which have been strongly sticky since ancient times.
Consumer preferences gradually changed to liquid hair styling products and polymer-based hair styling products that do not have a sticky feeling or odor of raw materials over time, and these are now the mainstream of hair styling products. The polymer-containing hair styling material is a non-oil hair styling material that uses gums, resins, etc. as a base, but at present, most of them use a synthetic resin compound having excellent stability as a base.

As synthetic resin compounds, nonionic, anionic, cationic, or amphoteric resins are used. In particular, nonionic resin compounds such as polyvinylpyrrolidone and polyvinyl methyl ether form a hard film and can exhibit a strong setting force, and are therefore widely used in hard type hair styling products. On the other hand, anionic polymer compounds such as vinyl methyl ether / monoethyl maleate copolymer are also used as a hairdressing base. Further, vinylpyrrolidone / N, N-dimethylaminoethyl methacrylic acid copolymer sulfate is used as the cationic polymer compound, and polymethacrylate ester ethanol solution is used as the amphoteric polymer compound as a hair dressing base. Are used respectively.

[0004]

However, with the above-mentioned nonionic resin compounds represented by polyvinylpyrrolidone, there is a problem that the flaking phenomenon is likely to occur while the strong setting force can be exhibited. Moreover,
Since the compound itself has hygroscopicity, there is a problem that a film formed at high temperature and high humidity becomes too soft, and a decrease in setting force and a sticky feeling are observed. Further, the anionic polymer compound is not easily affected by humidity, but has a problem that it has a low affinity for hair and a flaking phenomenon easily occurs. Furthermore, since it is an anionic type, the addition of a cationic substance is limited, and there is a risk that the hair solidifying phenomenon may occur due to the use of a rinse agent during hair washing. On the other hand, the cationic polymer compound has a problem of safety such as toxicity and skin irritation and a problem that a solidification phenomenon occurs on the hair during washing. Further, the amphoteric polymer compound has an advantage that the flaking phenomenon is unlikely to occur, but has a problem that it is not possible to exhibit high set retention under high humidity conditions.

[0005] Therefore, in the industry, it is possible to give a good texture with elasticity and elasticity to the hair, and at the same time, the setting property is good and the set holding property is extremely excellent even under a high humidity condition. It has been desired to create an excellent hair cosmetic composition that can be expressed and does not cause flaking or the like and can form a film having good hardness on the hair surface after application.

[0006]

In the present invention, the general formula 3
An amphoteric polymer compound having a molecular weight of 50,000 to 500,000 represented by (Chemical Formula 3) and a water-soluble oily oligomer having a molecular weight of 500 to 10,000 represented by the general formula 4 (Chemical Formula 4) are contained as essential components. By providing a hair cosmetic composition capable of solving the above problems, the conventional problems described above are solved.

[Chemical 3] (However, in the formula, n and m represent natural numbers, and the ratio of these n and m is in the range of 70:30 to 20:80, and R
₁ and R ₅ are a hydrogen atom or a methyl group, R ₂ and R ₃ are alkyl groups each having 1 to 4 hydrocarbons, R ₄ and R
₇ represents an alkylene group having 1 to 4 carbon atoms, R ₆ represents a saturated or unsaturated alkyl group having 1 to 24 carbon atoms, and A represents an oxygen atom or an NH group. )

[Chemical 4] (However, in the formula, p and q are natural numbers, and the ratio of p and q is in the range of 9: 1 to 1: 9.)

[0007]

The constitution of the hair cosmetic composition according to the present invention will be described below. In the present invention, the specific amphoteric polymer compound and the water-soluble oily oligomer are used as essential components. As the amphoteric polymer compound used as one of the essential components, a copolymer having a betaine structural unit represented by the general formula 5 (formula 5) and having a molecular weight of 50,000 to 500,000 is used.

[Chemical 5] (However, in the formula, n and m represent natural numbers, and the ratio of these n and m is in the range of 70:30 to 20:80, and R
₁ and R ₅ are a hydrogen atom or a methyl group, R ₂ and R ₃ are alkyl groups each having 1 to 4 hydrocarbons, R ₄ and R
₇ represents an alkylene group having 1 to 4 carbon atoms, R ₆ represents a saturated or unsaturated alkyl group having 1 to 24 carbon atoms, and A represents an oxygen atom or an NH group. )

This copolymer is obtained by, for example, dialkylaminoethyl acrylate such as dimethylaminoethyl acrylate and diethylaminoethyl acrylate, or dialkylaminoethyl methacrylate such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, and diacetone acrylamide. Acrylic acid alkyl ester such as acid, methyl acrylate, ethyl acrylate, isobutyl acrylate, allyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, oleyl acrylate, stearyl acrylate, cyclohexyl acrylate, or methacrylic acid, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, allyl Methacrylate, 2-eth Copolymerizing hexyl methacrylate and methacrylic acid alkyl esters, those obtained by treatment with appropriate amphoteric agent can be suitably used. As the amphoteric agent, halogenated acetic acid salts such as alkali metal salts of halogenated acetic acid, ammonium salts, and amine salts are preferably used, and specifically, potassium monochloroacetate, sodium monochloroacetate, potassium monobromopropionate. Etc. are exemplified, but not particularly limited.

The molecular weight of this amphoteric polymer is 5
It is set within the range of 0000 to 500000. here,
The reason why the molecular weight of the amphoteric polymer compound is set in the above range is that when the molecular weight is less than 50,000, the hardness of the formed film is low and a satisfactory setting force cannot be obtained, while the molecular weight exceeds 500000. This is because the hardness of the film becomes too high and the desired feeling of use and finish cannot be obtained, which is not preferable in any case. More preferably, the molecular weight is 60,000 to 200,000.
A range of about 10 is preferable since it has a film hardness suitable for a hair styling agent, but is not particularly limited.

The amphoteric polymer compound includes a monomer having a betaine structure represented by the general formula 6 (chemical formula 6) contained as a monomer and an ester-based monomer represented by the general formula 7 (chemical formula 7). The degree of polymerization is 70:30 to 2
The range is 0:80, and more preferably 60: 40-3.
It is desirable that the range is 0:70.

[0011]

[Chemical 6] (However, in the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ , R ₃
Is an alkyl group each having 1 to 4 hydrocarbons, R
₄ , R ₇ is an alkylene group having 1 to 4 carbon atoms,
A represents an oxygen atom or an NH group. )

[Chemical 7] (However, in the formula, R ₅ is a hydrogen atom or a methyl group, and R ₆ is 1 to
It represents a saturated or unsaturated alkyl group having 24 carbon atoms. )

The reason for this is that when the monomer having the betaine structure is polymerized in the polymer copolymer in an amount of more than 70 with respect to the ester monomer 30, a film formed by the polymer copolymer. Of the betaine structure is less than 20 polymerized with respect to the ester-based monomer 80, it becomes poorly soluble in water and water. It is not preferable in any case because it cannot be blended in a system having a small amount of hair and the wash-off during hair washing becomes poor. Further, the polymerization ratio of the monomer having a betaine structure and the ester-based monomer is 60:40 to 3
The ratio of 0:70 is preferable because it has a better setting force and can be applied to various dosage forms.

More specifically, such an amphoteric polymer compound is N-methacryloyloxyethyl N, N-dimethylammonium α-N represented by the general formula 8 (formula 8).
-Methylcarboxybetaine / butyl methacrylate copolymer can be exemplified as a preferred example, and as an example thereof, Yucaformer AM-75 (trade name, manufactured by Mitsubishi Petrochemical Co., Ltd.) can be mentioned.

[Chemical 8]

The above-mentioned amphoteric polymer compound is blended as a base of a setting agent for hair. It is desirable that the amount of this compound is 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, in the hair cosmetic composition. The reason for this is that if the amount of the amphoteric polymer compound is less than 0.1% by weight, the setting power for hair is insufficient, while
Even if it is blended in an amount of more than 0% by weight, the effect proportional to the blending amount is not exhibited, and conversely, flaking occurs on the applied hair, and an undesired phenomenon occurs in the formed film. Is caused, which is not preferable in any case. Furthermore, especially by blending the amphoteric polymer compound in the range of 0.5 to 5% by weight, it is possible to impart a good texture with elasticity and elasticity to the hair, which is the object of the present invention. Moreover, it is possible to exhibit an excellent set retention property under high humidity.

On the other hand, in the present invention, a water-soluble oily oligomer is contained as an essential component together with the amphoteric polymer compound. As the water-soluble oily oligomer, a methoxyethyl acrylate / hydroxyethyl acrylate copolymer having a molecular weight of 500 to 10,000 represented by the general formula 9 (Formula 9) is used.

[Chemical 9] (In the formula, p and q are natural numbers, and the ratio of p and q is 9: 1 to 1: 9.)

The water-soluble oily oligomer has a molecular weight of 500 to 10,000, more preferably 100.
Those in the range of 0 to 5000 are preferable. The reason is that when the molecular weight of the water-soluble oily oligomer is less than 500,
This is because elasticity cannot be imparted, while the molecular weight is 10
If it exceeds 000, stiffening occurs, which is not preferable in any case. Especially the molecular weight is 1000-5
It is more preferable to use one having a range of 000 because it exhibits excellent elasticity and setting force.

Further, the ratio (p: q) of the degree of polymerization of methoxyethyl acrylate monomer forming a water-soluble oily oligomer and hydroxyethyl acrylate monomer is:
The range is from 9: 1 to 1: 9. The reason for this is that if the methoxyethyl acrylate monomer in the oligomer is polymerized in excess of 9 times the hydroxyethyl acrylate monomer, the solubility in water will decrease, while the hydroxy acrylate monomer If less than 1/9 is polymerized with respect to the ethyl monomer, elasticity cannot be imparted, which is not preferable in any case. More preferably, an oligomer having a p: q ratio of 2: 8 to 8: 2 imparts excellent elasticity and is excellent in solubility, and thus is most preferable, but is not particularly limited. As such a water-soluble oily oligomer, more specifically, PLUS SIZE L-201 (trade name, manufactured by Kyowa Kagaku Co., Ltd.) can be mentioned.

The water-soluble oily oligomer as described above is blended with the above-mentioned amphoteric polymer compound to exhibit a set-holding property on hair. It is desirable that this blending amount be in the range of 1:20 to 3:10, and more preferably 1:10 to 2:10, with respect to the blending amount of the amphoteric polymer compound.
The reason for this is that when the amount of the water-soluble oily oligomer is less than 1/20 parts by weight with respect to the amphoteric polymer, the effect of improving the set holding power is not exhibited, while when it exceeds 3/10 parts by weight. This is because, when compounded in such a manner, the holding power for the set is lowered, which is not preferable in any case.

In addition to the essential components of the amphoteric polymer compound and the water-soluble oily oligomer as described above, in the present invention, a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant are used. , Polyhydric alcohols, gums, oily substances, silicones, water-soluble polymer compounds and their derivatives, preservatives, chelating agents, antioxidants,
Known additives used as hair cosmetics, such as ultraviolet absorbers, pigments, and fragrances, can be optionally used in combination as long as the effects of the present invention are not impaired.

Furthermore, the hair cosmetic composition of the present invention can be prepared as a spray-type or dispenser-type or foam-type hair styling agent, and the form is a solution-type,
It can be prepared in any dosage form such as uniform dispersion or non-uniform dispersion.

[0021]

[Prescription Example] The hair cosmetic composition according to the present invention will be more specifically described below with reference to prescription examples. However, the present invention is not limited to the following formulation examples.
(In the following formulation examples, the amphoteric polymer compound means N
-Methacryloyloxyethyl N, N-dimethylammonium α-N-methylcarboxybetaine / butyl methacrylate copolymer, and the water-soluble oily oligomer represent methoxyethyl acrylate / hydroxyethyl acrylate copolymer. )

(Formulation Example 1) Part by weight of foamy hair styling agent (aerosol type) (content liquid) Amphoteric polymer compound (molecular weight 150,000) 2.0 Water-soluble oily oligomer (molecular weight 1500) 0.3 Stearyl trimethyl ammonium chloride 3 Polyoxyethylene lauryl ether (EO.2) 0.1 Perfume 0.1 Methylparaben 0.1 Ethanol 5.0 Purified water Remainder 100.0 LPG gas (at 20 ° C.) against the above content liquid A foamy hair styling product was prepared by blending a vapor pressure of 4.0 Kg / cm ² ) as follows. Weight part Contents liquid 92.0 LPG 8.0 100.0

(Formulation Example 2) Mist-shaped hair styling agent (dispenser type) weight part Amphoteric polymer compound (molecular weight 70000) 5.0 Water-soluble oily oligomer (molecular weight 2000) 0.5 Polyoxyethylene hydrogenated castor oil (E.0) .60) 0.1 Fragrance 0.1 Ethanol 20.0 Purified water Balance 100.0

[0024]

[Examples] The effects of the hair cosmetic composition according to the present invention will be further clarified below with reference to Examples. However,
The present invention is not limited to the following examples.

Examples 1 to 6 and Comparative Examples 1 to 6 As an amphoteric polymer compound, N-methacryloyloxyethyl N, N-dimethylammonium α-N-methylcarboxybetaine / butyl methacrylate copolymer [trade name] Yuka Former AM75 (manufactured by Mitsubishi Petrochemical Co., Ltd.) is used as a water-soluble oily oligomer, and a methoxyethyl acrylate / hydroxyethyl acrylate copolymer [trade name: Plus Size L-201 (Kyoto Chemical ( The hair cosmetic compositions of Examples 1 to 6 were prepared according to the formulations shown in Table 1 by using each of the above). In addition, the amphoteric polymer compound, the water-soluble oily oligomer, and the acrylic resin alkanolamine liquid [trade name: Plus Size L-6330 (manufactured by Mutual Chemistry Co., Ltd.)] as anionic resin were prepared according to the formulations shown in Table 2. By blending, hair cosmetic compositions of Comparative Examples 1 to 6 were prepared.

[Table 1]

[Table 2]

[0026]

[Test Examples] Using the hair cosmetic compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 6, the following stiffening and elasticity tests, setting force tests, and set holding force tests were conducted.
A hair flaking generation test was performed. The results are shown in Tables 3 to 4.

[0027]

[Table 3]

[Table 4]

(1) Rigidity and Elasticity Test Approximately 3 g of the hair cosmetic composition obtained in Examples and Comparative Examples was evaluated by a sensory test when 20 panelists applied it directly to the hair. . Those that are not stiff and have sufficient elasticity are ◎, those that are not stiff and have elasticity are 〇, those that are not stiff but have no elasticity are △, and those that are stiff and have no elasticity are ×. They were evaluated, and the most common answer was adopted as the result of the stiffness test and elasticity test.

(2) Setting force test 150 μl of each hair cosmetic composition obtained in the above Examples and Comparative Examples was applied to a hair bundle having a weight of about 0.4 g and a length of about 10 cm, and the temperature was 23 ° C. and RH 60%. It was dried in the atmosphere of 5 hours or more. The bending rigidity of the hair bundle after drying was used as an index of the setting force. The bending rigidity was measured using a pure bending tester (KES-FB2 / manufactured by Kato Tech Co., Ltd.). (Note that the larger the numerical value of the bending rigidity obtained, the higher the setting force.)
Regarding the evaluation of the setting force, the bending rigidity value is 120 gf
cm ² or more at which things ◎, 100~120gf · cm
What is less than ² 〇, what is less than 50~100gf · cm ² △, × those less than 50 gf · cm ²
And evaluated respectively.

(3)Set holding power test Hair bundles weighing about 2 g and about 30 cm were obtained in Examples and Comparative Examples.
Dipped in 20 ml of each hair cosmetic composition for 30 seconds
Then, wrap it around a glass tube with a diameter of 1 cm and leave it in this state.
It was left to dry completely. After drying, remove the tufts from the glass tube.
Remove the apparent length of the hair bundle (L₀) Was measured. Next
Then, tie this bundle of hair in a thermo-hygrostat at a temperature of 35 ° C and a humidity of 80%.
Then, after 2 hours, take it out and again, the apparent length of the hair bundle
(L₁) Was measured. Based on the following formula from the obtained measured values
Then, the set holding power of each cosmetic composition was calculated.
(Note that the closer this value is to 100, the stronger the set holding power.
Indicates that. ) The calculated set retention (%) value is 85 or more
◎, 75 to less than 85 ○, 70 to 75
Less than 70 is evaluated as △ and less than 70 is evaluated as ×.
It was

(4) Flaking generation test of hair A hair bundle having a weight of about 1 g and a length of about 11 cm was dipped in 20 ml of each hair cosmetic composition obtained in the above-mentioned Examples and Comparative Examples, and 25 ° C. And left to dry for 24 hours. With respect to the hair bundle after drying, the occurrence of flaking phenomenon was visually evaluated, and ◎ means very good, ◯ means good.
Somewhat good was evaluated as Δ, and some were evaluated as ×.

(5) Film Hardness Approximately 0.1 g of each hair cosmetic composition of the above Examples and Comparative Examples
Was evenly spread over the surface of the slide glass and applied, and then dried at 70 ° C. for 30 minutes. After drying, it was left to cool in a desiccator, and the hardness of the formed film was measured. For hardness measurement, a pencil (trade name: Uni) manufactured by Mitsubishi Pencil Co., Ltd. was used, and 4 was applied to the film formed on the surface of the slide glass.
A method of applying a load of about 1 Kg at an angle of 5 degrees and observing whether the film is scratched or not was adopted. The hardness of the pencil when the film was scratched was taken as the result of the film hardness. Regarding the hardness of the film, ◎ is 3F or less, F to 2F
Was evaluated as 0, 2H to H was evaluated as Δ, and 3H or more was evaluated as x.

As is clear from the results of the above-mentioned test examples, the composition (comparative example 1) containing the amphoteric polymer compound but not containing the water-soluble oily oligomer has no stiffening of the hair after the treatment. , Although it is elastic, the flaking property is poor, and the set force and set retention are not sufficient.
Further, in the composition (Comparative Example 2) in which the amount of the water-soluble oily oligomer added was more than 3:10 with respect to the amphoteric polymer compound, the composition was stiff, elastic, and set-holding power under high humidity. It turns out that is not enough. Furthermore, it can be seen that the composition having a too small amount of the water-soluble oily oligomer (Comparative Example 3) has a poor flaking property. It can be seen that in the composition (comparative example 4) in which the amphoteric polymer compound was not used and the anionic resin and the water-soluble oily oligomer were used in combination, the hair after application was stiff and had no elasticity. It can be seen that the composition using only the amphoteric polymer compound and the anionic resin without adding the water-soluble oil oligomer (Comparative Example 5) has poor flaking properties and film hardness. It can be seen that the composition using only the water-soluble oil oligomer (Comparative Example 6) has poor set force and set retention under high humidity.

[0034]

As described above in detail, the present invention has the general formula 1
0 (Chemical formula 10)
0 is an amphoteric polymer compound and a water-soluble oily oligomer having a molecular weight of 500 to 10,000 represented by the general formula 11 (Chemical formula 11) is contained as an essential component, so that a hair cosmetic composition is obtained. As is clear from the results of the above-mentioned test examples, the hair after application imparts a good texture with elasticity without stiffening, and has good settability and settability under high humidity, and further flaking. It has an excellent effect that it is an excellent hair cosmetic composition capable of forming a film that is hard to occur and has good hardness on the surface of hair.

[Chemical 10] (However, in the formula, n and m represent natural numbers, and the ratio of these n and m is in the range of 70:30 to 20:80, and R
₁ and R ₅ are a hydrogen atom or a methyl group, R ₂ and R ₃ are alkyl groups each having 1 to 4 hydrocarbons, R ₄ and R
₇ represents an alkylene group having 1 to 4 carbon atoms, R ₆ represents a saturated or unsaturated alkyl group having 1 to 24 carbon atoms, and A represents an oxygen atom or an NH group. )

[Chemical 11] (However, in the formula, p and q are natural numbers, and the ratio of p and q is in the range of 9: 1 to 1: 9.)

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Noriyuki Fujiwara 5-12, 12kencho, Chuo-ku, Osaka City Mandom Central Research Institute, Inc.

Claims (1)

[Claims] 1. A molecular weight of 50 represented by the general formula 1 (Formula 1).
000 to 500,000 amphoteric polymer compounds and the general formula 2
A hair cosmetic composition comprising a water-soluble oily oligomer having a molecular weight of 500 to 10,000 represented by (Chemical Formula 2) as an essential component. [Chemical 1] (However, in the formula, n and m represent natural numbers, and the ratio of these n and m is in the range of 70:30 to 20:80, and R
₁ and R ₅ are a hydrogen atom or a methyl group, R ₂ and R ₃ are alkyl groups each having 1 to 4 hydrocarbons, R ₄ and R
₇ represents an alkylene group having 1 to 4 carbon atoms, R ₆ represents a saturated or unsaturated alkyl group having 1 to 24 carbon atoms, and A represents an oxygen atom or an NH group. ) [Chemical 2] (However, in the formula, p and q are natural numbers, and the ratio of p and q is in the range of 9: 1 to 1: 9.)